Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
  • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
  • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
  • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
  • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
  • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes

Definitions

• the present invention relates to a release paper or release film resin composition, and a release paper or release film obtained by curing the same.
• a release agent is applied to the surface of a sheet-shaped base material such as paper or plastic to form a cured film, which imparts release properties to adhesive or tacky substances.
• Release paper and release film have a wide variety of uses, and may be used for sticky substances such as labels, stickers, and tapes, or for the molding process of non-sticky substances such as ceramics layers and urethane resins. Yes, different performance is required depending on the application.
• An example of a process used for molding non-sticky materials is process paper for manufacturing synthetic leather.
• a release paper is cured on a base material to form a process paper, and a urethane resin, a vinyl chloride resin, a polyamide resin, a polyamino acid resin or the like is applied to the process paper and dried.
• An adhesive layer is formed on the dried resin, a base cloth is attached to the dried resin, and the resin is peeled off from the process paper to produce synthetic leather.
• polypropylene As a resin composition for making the surface of synthetic leather process paper releasable, polypropylene, aminoalkyd resin/aminoacrylic resin, and silicone are known to be representative three types.
• Polypropylene type has excellent durability of releasability when repeatedly used, but there is a limit to use at relatively high temperature, in which case the release surface is easily scratched, and enamel type It has the drawback that it is not suitable for synthetic leather.
• Amino alkyd resin/amino acrylic resin-based products have excellent gloss, but poor peelability.
• Silicone-based materials have excellent releasability, but are not suitable for enamel-type synthetic leather because of their poor gloss.
• Patent Document 1 JP-A-56-14550 discloses that 15 to 50 mol% of organic groups bonded to a silicon atom in one molecule are phenyl groups, and the remaining organic groups.
• a resin composition for process release paper which comprises a silicone-modified acrylic resin modified with an organopolysiloxane in which at least one of the groups is a hydroxy group-substituted organic group, and a polyisocyanate compound. Then, "the use of a hydroxy group-substituted organic group makes it possible to obtain a process release paper having excellent heat resistance, good gloss, and good releasability.”
• Patent Document 2 JP-A-56-11980
• 15 to 50 mol% of organic groups bonded to silicon atoms in one molecule are phenyl groups, and at least one of the remaining organic groups is hydroxy.
• a resin composition for process release paper which comprises a silicone-modified alkyd resin modified with an organopolysiloxane which is a group-substituted organic group, and a polyisocyanate compound is disclosed. Then, it is described that "a process release paper using an alkyd resin can be obtained which is excellent in heat resistance, has good gloss, and has good releasability.”
• Patent Document 3 JP-A-56-14566
• 15 to 50 mol% of organic groups bonded to silicon atoms in one molecule are phenyl groups, and at least one of the remaining organic groups is substituted with a hydroxy group.
• a resin composition for process release paper which comprises a silicone-modified acrylic resin modified with an organopolysiloxane which is an organic group, an alkanol-modified amino resin, and an acidic catalyst. Then, "the acidic catalyst makes it possible to obtain a process release paper having excellent heat resistance, good gloss, and good releasability even in a process release paper containing both an acrylic resin and an amino resin.” ing.
• Patent Document 4 JP-A-3-263475), a methyl group, a phenyl group and an organic group are bonded to a silicon atom, and at least one of the organic groups is a hydroxy group-substituted organic group, which is bonded to the silicon atom.
• a resin composition for process release paper which comprises a silicone-modified alkyd resin modified with an organopolysiloxane in which 15 to 50 mol% of all substituents are phenyl groups, an alkanol-modified amino resin, and an acidic catalyst. .. Then, it is possible to obtain a process release paper having excellent heat resistance, good gloss, and good releasability even in a process release paper containing both an alkyd resin and an amino resin with an acidic catalyst. There is.
• Patent Document 5 JP-A-2-28242
• an alkyd resin or an acrylic resin and 15 to 50 mol% of silicon atom-bonded organic groups in one molecule are phenyl groups, and at least 1 of the remaining organic groups is used.
• a resin composition for process release paper which comprises an organopolysiloxane having a hydroxy group-substituted organic group, an alkanol-modified amino resin, and an acidic catalyst is disclosed. Then, "the process release paper obtained with this resin composition for process release paper has excellent releasability, heat resistance, good gloss, and can suppress variations in quality, as compared with the conventional process release papers. .” is described.
• Patent Document 6 Japanese Patent No. 5282083 discloses that the hydroxyl value is 10 to 150 mgKOH/g, the glass transition temperature is 20 to 100° C., and the weight average molecular weight is 20,000 to 100,000.
• a release agent composition comprising a hydroxy group-containing acrylic resin, an amino resin, and a silicone resin having a functional group capable of chemically bonding to at least one of the hydroxy group-containing acrylic resin and the amino resin. Has been done. Then, it is described as "excellent in peelability at high temperature, gloss, surface condition, and repeated durability".
• the amino alkyd resin/amino acrylic resin type release agent has improved gloss, heat resistance and release property, and has achieved a certain effect.
• the aminoalkyd resin/aminoacrylic resin-based release agent has a drawback that the curing is slow, and improvement of curability has not been studied. In recent years, in order to improve the production efficiency of process paper, curability in a short time or at a low temperature is required, which is an important issue.
• Patent Document 7 JP-A-2000-095929 discloses a silicone containing an alkyd resin, an amino resin, the alkyd resin and a functional group reactive with the amino resin.
• a resin wherein the amino resin, a methylated melamine resin containing one or more methylol groups per triazine nucleus, a release agent composition for a step release paper containing as a main component is disclosed. It is useful for the production of process release paper that has excellent releasability, gloss, surface condition, and reusability, and can be cured and dried at low temperatures.”
• the present invention has been made in view of the above circumstances, and provides a resin composition for a release paper or release film, which has good releasability and repetitive durability, excellent curability at low temperature, and excellent storage stability. The purpose is to
• the present invention provides the following inventions. 1.
• the resin composition for a release paper or release film according to 1 or 2 wherein the blending amount of the component (D) is 10 to 200 parts by mass based on 100 parts by mass of the total of the components (A) to (C).
• the resin composition for release paper or release film of the present invention has good releasability and repeated durability, excellent curability at low temperature, and good storage stability.
• composition for release paper or release film may be simply abbreviated as “composition”.
• component (A) of the present invention is a resin selected from (A-1) hydroxy group-containing acrylic resin and (A-2) alkyd resin, and may be used alone or in combination of two or more kinds. ..
• the (A-1) hydroxy group-containing acrylic resin is not particularly limited as long as it is an acrylic resin having one or more hydroxy groups in one molecule, but it has one or more hydroxy groups in one molecule and is radically polymerizable. Radical-polymerizable monomer (A-1-a) having 1 or more groups in 1 minute and radical-polymerizing monomer having 1 or more radical-polymerizable groups in 1 minute without having a hydroxy group in 1 molecule. A copolymer with the monomer (A-1-b) is preferable.
• the component (A-1-a) used in the present invention is particularly preferably a radical-polymerizable monomer having one or more hydroxy groups in one molecule and one or more radical-polymerizable groups per minute.
• a radical-polymerizable monomer having one or more hydroxy groups in one molecule and one or more radical-polymerizable groups per minute.
• the radical polymerizable group include radical polymerizable groups such as an acrylic group, a methacrylic group, a styryl group, a cinnamic acid ester group, a vinyl group and an allyl group.
• 2-hydroxyethyl (meth)acrylate 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3phenoxypropyl (meth)acrylate, 1,4-cyclohexanediacrylate
• Examples include methanol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and Praxel F series (manufactured by Daicel Corporation) modified with caprolactone.
• the component (A-1-b) used in the present invention is not particularly limited as long as it is a radical-polymerizable monomer that does not have a hydroxy group in one molecule and has one or more radical-polymerizable groups per minute. Alternatively, one kind may be used alone, or two or more kinds may be appropriately combined and used.
• a compound having one radical-polymerizable group such as an acrylic group, a methacrylic group, a styryl group, a cinnamic acid ester group, a vinyl group, and an allyl group in one molecule
• the polymerization ratio of the (A-1-a) component and the (A-1-b) component is adjusted according to the hydroxyl value of the hydroxy group-containing acrylic resin.
• the hydroxy group-containing acrylic resin obtained by polymerization preferably has a hydroxyl value of 20 to 200 mgKOH/g, more preferably 30 to 190 mgKOH/g, and further preferably 40 to 180 mgKOH/g.
• the hydroxyl value of the hydroxy group-containing acrylic resin is a value measured according to the neutralization titration method (JIS K0070).
• the copolymerization of the monomer raw material containing the component (A-1-a) and the component (A-1-b) is performed by using benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, tert-butyl 2-ethylperoxyhexanoate, etc.
• an ordinary radical polymerization initiator such as peroxides and azo compounds such as 2,2′-azobis(2-methylbutyronitrile
• solution polymerization method emulsion polymerization method
• suspension Any of a polymerization method and a bulk polymerization method can be applied.
• the solution polymerization method is preferable because it is easy to adjust the weight average molecular weight of the (A-1) hydroxy group-containing acrylic resin to the optimum range.
• aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; ethanol.
• Monohydric alcohols such as isopropanol, n-butanol, and isobutanol, etc. can be used alone or in combination of two or more.
• Alkyd resin refers to a synthetic resin obtained by polycondensation and transesterification of a polyhydric alcohol and a polybasic acid with a fatty acid or a fatty oil.
• alkyd resin a commercially available one may be used, or it may be synthesized according to a conventionally known method.
• polyhydric alcohol examples include, for example, ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 2,3-butane.
• dihydric alcohols such as adducts
• trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and tris-(2-hydroxyethyl)isocyanurate.
• These polyhydric alcohols can be used alone or in combination of two or more kinds. Above all, it is preferable to use a di
• the polybasic acid include, for example, saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid, sebacic acid; maleic acid, maleic anhydride, fumaric acid.
• unsaturated polybasic acids such as acid, itaconic acid, citraconic anhydride, isophthalic acid and trimellitic anhydride; cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, rosin-maleic anhydride adduct, etc.
• examples thereof include polybasic acids by the Diels-Alder reaction.
• benzoic acid which is a monobasic acid may be used in combination.
• fatty acid or fatty oil examples include animal and vegetable oils such as safflower oil, chrysanthemum oil, morning glory oil, edible oil, tall oil, rice bran oil, castor oil, dehydrated castor oil, rapeseed oil, cottonseed oil, coconut oil, fish oil, squid liver oil, and these fatty acids. ..
• alkyd resins can be used.
• an alkyd resin having an oil length of 0 to 65, preferably 25 to 55, or an animal or vegetable oil fatty acid, or one produced by using various saturated fatty acids may be used.
• alkyd resins examples include Alkydia 1307-60-EL, Alkydia 1308-E, Alkydia ER-4005-60, Alkydia EZ-3065-P, Alkydia EZ-3509-60, Alkydia EZ-3801-60, Alkydia OD-E-198-50, Alkydia OD-E-230-70, Alkydia OD-E-230-70E, Alkydia J-524-A (above, manufactured by DIC Corporation), Arachid IA-120-60L, Arachid 1782-60, Araquid 3101X-60 (above, manufactured by Arakawa Chemical Industry Co., Ltd.), Hariftar 732-60, Hariftar 915-60L, Hariftar COG40-50T, Hariftar SB-7150X, Hariftar SB-7540 (Harima Chemical Group Co., Ltd.) Etc.
• the weight average molecular weight of the component (A) is preferably from 3,000 to 400,000, more preferably from 5,000 to 350,000, even more preferably from 7,000 to 300,000. When the weight average molecular weight is within the above range, coating properties and handling properties are good.
• the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (hereinafter abbreviated as "GPC") using tetrahydrofuran as a developing solvent.
• the component (B) is a resin selected from a full ether type methylated melamine resin, a methylol type methylated melamine resin, and a polymer thereof, and can be used alone or in combination of two or more kinds.
• the component (B) in the present invention has a structure in which a functional group is bound around the triazine ring via three nitrogen atoms.
• the component (B) serves as a crosslinking agent that reacts with the component (A) and/or the component (C).
• Melamine resin is a synthetic resin obtained by condensing melamine and formaldehyde, and is a condensate composed of monomers or multimers of dimers or higher. It has an imino group, a methylol group or an alkoxymethyl group as a functional group in one molecule, and is classified into a full ether type, a methylol type, an imino type and a methylol/imino type depending on the functional group.
• melamine resins are classified according to the type of alkoxymethyl group, melamine resins in which all alkoxymethyl groups are methoxymethyl groups are methylated melamine resins, and melamine resins in which all alkoxymethyl groups are n-butoxymethyl groups are n
• a melamine resin that is a butylated melamine resin in which a methoxymethyl group and an n-butoxymethyl group are mixed in an alkoxymethyl group is a methylated/n-butylated melamine resin.
• the component (B) in the present invention is excellent in peelability, repetitive durability and curability, a full ether type methylated melamine resin, a methylol type methylated melamine resin, and a multimer thereof are used. Methylated melamine resins and multimers thereof are preferred.
• the component (B) in the present invention may be a commercially available product or may be synthesized according to a conventionally known method.
• Examples of commercially available products include Cymel 300, Cymel 303LF, Cymel 350, Cymel 370N (all manufactured by Ornex Japan Co., Ltd.), Nicarak MW-30M, Nicarak MW-30 (all manufactured by Nippon Carbide Industry Co., Ltd.) and the like. Can be mentioned.
• the blending amount of the component (B) is 10 to 120 parts by mass, preferably 12 to 110 parts by mass, and more preferably 14 to 100 parts by mass, relative to 100 parts by mass of the component (A). Within the above range, the releasability and the curability are good, and the repeated durability is excellent.
• the component (C) of the present invention is an organopolysiloxane having two or more functional groups in one molecule that can chemically bond with one or more resins selected from the components (A) and (B). They may be used alone or in combination of two or more.
• Two or more functional groups capable of chemically bonding to one or more resins selected from the above-mentioned components (A) and (B) must be contained in one molecule.
• the (A) resin and the (B) resin forming the release layer and the silicone resin as the release component are chemically bonded in the release layer to form a silicone resin for the pressure-sensitive adhesive layer.
• Examples of such a functional group include a hydroxy group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and the like.
• a hydroxy group and an epoxy group are preferable, and a hydroxy group is more preferable.
• the organopolysiloxane may have either a linear structure or a branched structure as long as the effects of the present invention can be exhibited, but it may be represented by the following average composition formula (1). preferable.
• R 1 may be the same or different and is an unsubstituted or substituted organic group having 1 to 20 carbon atoms, which has a hydroxy group, an amino group, a carboxyl group, an epoxy group or an isocyanate group, and is a hetero atom.
• a is 2 or more, b is 1 or more, c is 0 or more, d is an integer of 0 or more, and 5 ⁇ a+b+c+d. ⁇ 500.
• Preferred examples of the organic group having 1 to 20 carbon atoms include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group and butyl group, and 5 to 8 carbon atoms such as cyclohexyl group. Examples thereof include an aryl group having 6 to 10 carbon atoms such as a cycloalkyl group, a phenyl group and a tolyl group, and an aralkyl group having 7 to 10 carbon atoms such as a benzyl group.
• Examples of the organic group having 1 to 20 carbon atoms which has a hydroxy group, an amino group, a carboxyl group, an epoxy group or an isocyanate group and may be substituted with a hetero atom, include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group and a hydroxybutyl group.
• hydroxypentyl group hydroxyhexyl group, hydroxyheptyl group, hydroxyoctyl group and other hydroxyalkyl groups
• a hydroxyalkyl group, a polyethylene glycol group, and a polypropylene glycol group are more preferable from the viewpoint of curability.
• R 1 5 to 50 mol% is preferably an aryl group or an aralkyl group, and more preferably 10 to 40 mol% is an aryl group or an aralkyl group. Within the above range, the releasability is better.
• a, b, c, and d are such that a is 2 or more, preferably 2 to 30, b is 1 or more, preferably an integer of 1 to 500, and c is 0 or more, preferably 0 to 10. Is an integer of 0 or more, preferably 0 to 10, and 5 ⁇ a+b+c+d ⁇ 500, preferably 10 ⁇ a+b+c+d ⁇ 400.
• the blending amount of the component (C) is 0.5 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the component (A). Within the above range, the releasability is excellent and the migration of silicone can be suppressed.
• the component (D) of the present invention is a monohydric alcohol having 1 to 8 carbon atoms, and can be used alone or in combination of two or more. By adding the component (D), the storage stability of the composition is improved.
• Examples of the monohydric alcohol having 1 to 8 carbon atoms include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methoxy Butanol, 3-methyl-3-methoxybutanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3- Pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 2-
• the compounding amount of the component (D) is 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, still more preferably 20 to 100 parts by mass, relative to 100 parts by mass of the total of the components (A) to (C). .. Within the above range, the storage stability is excellent.
• the melamine resin reacts with functional groups such as hydroxyl groups and reacts with other components by condensation reaction. This reaction is promoted by the addition of an acidic catalyst, but a crosslinked structure is formed when it reacts with a compound having two or more reactive groups in one molecule. Therefore, it is considered that the viscosity of the composition increases and the peel strength also changes.
• a specific amount of a monohydric alcohol having 1 to 8 carbon atoms to the total amount of components (A) to (C)
• a compound having two or more reactive groups in one molecule can be obtained. It is considered that the storage stability is improved because the reaction is suppressed.
• An acidic catalyst (E) can be used in the composition of the present invention from the viewpoint of accelerating the crosslinking reaction of the component (A), the component (B) and the component (C).
• the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, carboxylic acids such as acetic acid, monochloroacetic acid, dichloroacetic acid and butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, p -An organic acid selected from organic sulfonic acids such as phenol sulfonic acid, methane sulfonic acid and ethane sulfonic acid. These acidic catalysts may be used alone or in an appropriate combination of two or more.
• the amount of the catalyst that accelerates the reaction may be sufficient, and for example, 0.1 to 10 parts by mass is preferable with respect to 100 parts by mass of the total of the components (A) to (C), It is more preferably 0.5 to 5 parts by mass. Within the above range, the curability is excellent and the durability of the film is also good.
• [(F) component] In the composition of the present invention, an arbitrary amount of a solvent (excluding the component (D)) can be blended as the component (F) alone or in combination of two or more kinds. If necessary, it can be used as a solvent-type composition diluted with a solvent. By diluting with a solvent, practical advantages such as improvement of coating workability and improvement of coating film state such as coating film thickness and surface finish state can be obtained.
• Usable solvents include aromatic hydrocarbon compounds such as toluene and xylene; aliphatic hydrocarbon compounds such as hexane, heptane and isoparaffin; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate and butyl acetate.
• aromatic hydrocarbon compounds such as toluene and xylene
• aliphatic hydrocarbon compounds such as hexane, heptane and isoparaffin
• ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone
• ethyl acetate and butyl acetate examples thereof include ester compounds such as; ether compounds such as diisopropyl ether and 1,4-dioxane, but any compound can be used as long as it can be dissolved.
• the blending amount of the component (F) is preferably 100 to 20,000 parts by mass, more preferably 200 to 10,000 parts by mass, relative to 100 parts by mass of the component (A).
• the viscosity of the resin composition for release paper or release film of the present invention at 25° C. is preferably 0.1 mPa ⁇ s to 10 Pa ⁇ s, more preferably 0.2 mPa ⁇ s to 5 Pa ⁇ s, and more preferably 1 mPa ⁇ s to 3 Pa ⁇ s. Is more preferable. If the viscosity is 1 mPa or more, it is measured by a B-type rotational viscometer, and if it is less than 1 mPa, it is measured by an Ostwald viscometer.
• the composition of the present invention may be prepared by mixing the components (A) to (D) and, if necessary, the component (E), the component (F), and the optional component, but the components (A), (B), ( From the viewpoint of storage stability, a method in which C), (D), (F) and optional components are uniformly mixed in advance and then the component (E) is added immediately before use is preferable.
• the mixing method and the like are not particularly limited, and known methods can be used.
• the present invention provides a release paper or release film having a cured coating formed by applying the above-mentioned release paper or release film resin composition to a substrate and then heating.
• the release paper or release film resin composition as it is, or after further diluted with the above-mentioned solvent for dilution in the range described above, a comma coater, a lip coater, a roll coater, a die coater, a knife coater, a blade coater,
• a coating method such as rod coater, kiss coater, gravure coater, wire bar coater, screen coating, dip coating, cast coating, etc.
• a cured film can be formed on the substrate.
• the coating amount is preferably 0.01 ⁇ 100g / m 2, more preferably 0.03 ⁇ 20g / m 2, the temperature at the time of drying is preferably 50 ⁇ 200 ° C., more preferably 70 ⁇ 180 ° C..
• the time for drying is preferably 1 to 120 seconds, more preferably 5 to 90 seconds.
• the base material examples include polyethylene laminated paper, glassine paper, high-quality paper, kraft paper, clay-coated paper, various coated papers such as mirror-coated paper, synthetic paper such as YUPO, polyethylene film, polypropylene film such as CPP and OPP, polyethylene terephthalate.
• polyester films such as films, polyamide films, polyimide films, polylactic acid films, polyphenol films, and polycarbonate films.
• a base material surface having corona treatment, etching treatment, or plasma treatment may be used.
• a component (A-1) A glass reactor equipped with a stirrer, a thermometer, a reflux condenser, and a dropping device was charged with 40.0 parts by mass of toluene, heated to 90 to 100° C., and then 26.0 parts by mass of 2-hydroxyethyl methacrylate (0.
• Alkydia J-524-A manufactured by DIC: 60% by mass xylene solution of coconut oil modified alkyd resin
• C component (C component)
• C-1) Polyorganosiloxane represented by the general formula (2): The bonding order of each siloxane unit is not limited to the following, and Me is a methyl group and Ph is a phenyl group.
• C-2) Polyorganosiloxane represented by the general formula (3): The bonding order of each siloxane unit is not limited to the following.
• Examples 1 to 8 and Comparative Examples 1 to 8 Using the components (A) to (F) shown above as raw materials, a coating composition was prepared by the following procedure. The components (A), (B), (C), (D) and (F) were placed in a flask according to the compounding ratios shown in Tables 1 to 3 and mixed uniformly. Component (E) was added to the obtained solution according to the compounding ratios in Tables 1 to 3 and mixed with stirring to obtain a coating composition. Using this composition, a coated article was prepared and evaluated by the method described below.
• the obtained coating composition was applied to a mirror-coated paper having a thickness of 165 ⁇ m by a bar coater so that the coating amount was 5.0 g/m 2, and the coating was performed in a hot air dryer at 120° C. for 60 seconds and 120 seconds. After heating for 2 seconds to form a release agent layer, a one-component polyurethane solution [Krisbon 5516S (manufactured by Dainippon Ink and Chemicals, Inc.)] is applied to the surface of the cured film so that the thickness of the film becomes 30 ⁇ m. And heat treated at 130° C. for 2 minutes.
• a Knit-31B tape was attached to this treated surface, pressure-bonded back and forth once with a 2 kg roller, and after aging at 25° C. for 20 hours, the sample was cut into a width of 5 cm, and a tensile tester was used at an angle of 180°.
• the adhesive tape was pulled at a peeling speed of 0.3 m/min to measure the force (gf/50 mm) required for peeling.
• the peeling force after heating for 60 seconds is RA and the peeling force after heating for 120 seconds is RB.
• the peeling of the polyurethane was repeated 10 times under the above conditions, and the evaluation was performed.
• the peeling force at the third time was defined as RC.
• the numerical values in the table indicate the amount of the component (A), the amount of the component (B) including the solvent and the solution, and the amount of the component (A) and component (B) in the parentheses. did. "(B)/(A) 100 parts by mass”, “(C)/(A) 100 parts by mass”, “(D)/(A) to (C) total 100 parts by mass”, “(E)” /(A) 100 parts by mass” and “(F)/(A) 100 parts by mass” are described in terms of the pure content of each component, and the alcohol corresponding to the component (D) in the component (B). In addition, the solvent corresponding to the component (F) in the component (A) is included in the calculated value.

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• 2020
  • 2020-01-20 WO PCT/JP2020/001634 patent/WO2020153281A1/ja active Application Filing
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